Enhancement of the imprinting effect in cholesterol-imprinted microporous silica

A sol-gel method has been used to fabricate a cholesterol MIP for application in polar solutions. In this study, (cholesteryl propylcarbamate)triethoxysilane and tetraethyl orthosilicate were used as the hydrophobic monomer and crosslinker, respectively. The MIP had a larger pore volume when formation of the polymer was catalyzed at a higher pH than when it was formed at lower pH values, with the pore diameters being 3.5 nm and 2 nm, respectively for materials formed at high and low pH values. Both of these pore volumes were greater than those found for the respective control polymers formed without template. However, only the polymers formed at low pH values showed an imprinting effect. Compared with other methods explored, the sol-gel procedure gave only a small amount of non-specific binding for both the MIP and NIP when synthesized at low pH values. The largest imprinting-induced promotion of binding (IPB) value of the MIP (13 650%) was obtained with [HCl] = 0.01 M in the sol-gel solution. The MIP showed high selectivity towards cholesterol in comparison with other steroid hormones, and also to a lesser extent recognized vitamin D3 in methanol solution containing 5 vol.% water.     

改性聚苯乙烯微球的制备及其胶体晶体的组装

采用甲基丙烯酸改性的无皂乳液聚合方法制备了尺寸为210 nm、含羧基的聚苯乙烯(PS)微球，用红外光谱、透射电子显微镜和粒度分析仪对其形状和结构进行分析，结果表明，经甲基丙烯酸改性后得到了表面为高密度电荷的单分散性PS微球.用垂直沉积法快速制备出在较大范围(大于1 cm2)呈现很好有序性的密排结构聚苯乙烯胶体晶体薄膜，其在590 nm波长处存在光子带隙.在电子显微镜下，观察到这种胶体晶体是面心立方(fcc)密排结构.     

Development of β-hydroxyamide/titanium complexes for catalytic enantioselective silylcyanation of aldehydes

A highly enantioselective addition of trimethylsilylcyanide to aldehydes catalyzed by chiral titanium complexes is described. The chiral titanium complexes were prepared in situ from Ti(OⁱPr)₄ and β-hydroxyamide ligands, that could easily be synthesized from ketopinic acid and C₂ symmetrical chiral diamines in a small number of steps.     

Synthesis and thermotropic studies of a novel series of nematogenic liquid crystals 2-(6-alkoxynaphthalen-2-yl)-5-cyanopyridines

A novel series of highly birefringent liquid crystalline compounds, 2-(6-alkoxynaphthalen-2-yl)-5-cyanopyridines (nO-NpPyCN, n?=?2–8) that have potential as commercially useful, were synthesised using a short two-step reaction with overall yields between 55% and 85%. Spectral analyses were in accordance with the expected structures. Their thermotropic behaviours were investigated by polarising optical microscopy and differential scanning calorimetry. It was found that the desymmetrised core results in a nematic phase with a broad mesophase range.     

Ethanol effects on the gelation behavior of α-tocopherol acetate-encapsulated ethosomes with water-soluble polymers

This work aims at understanding the ethanol effects on the gelation behavior of ethosomes with the consideration of encapsulating a hydrophobic material. Gelation of the empty ethosomes by positively charged water-soluble polymers with and without hydrophobic modification, respectively, was systematically studied first for the effects of solution dielectric constant and gelator concentration on the phase map and rheological property of the mixtures. A comparison of the gelation behavior of empty and α-tocopherol acetate (α-TA)-encapsulated ethosomes sheds light on the possible influence of encapsulated hydrophobic material itself on the interaction between ethosomal lipid bilayers and gelator molecules. The experimental results revealed that ethosomes with an optimized amount of ethanol could result in a reasonable lifetime and encapsulation efficiency of more than 90 %. This is due to the effects of the solution dielectric constant on the formability of liposome and the partition of the hydrophobic material (α-TA) between ethosomal lipid bilayer and bulk phase. Moreover, the phase map and rheological property of the ethosome/polymer mixtures were found to be affected by the configuration of the polymer chain in aqueous ethanol solution. That is, the driving interactions between ethosomal lipid bilayers and gelator molecules were dominated by the hydrophobic material more than the electrostatic association. Finally, inclusion of a hydrophobic material, such as α-TA, in the ethosomes had less influence on the gelation behavior of the ethosomes with water-soluble polymers.     

Dislocation injection, reconstruction, and atomic transport on {001} Au terraces

High-resolution electron microscopy investigations of Au films show that adatoms on (100) surfaces insert into the underlying terrace to form surface dislocations. This injection readily occurs when the number of adatoms on a terrace is approximately 20 atoms or less. The surface dislocation glides along the terrace, but is repelled from the edges. The dislocation escapes by squeezing out in the dislocation line direction (not gliding out the terrace edge). Atomistic simulations confirm the dislocation stability, easy glide along the terrace and trapping at the terrace edge. These results have profound implications for film growth.     

静动干涉流动的分离涡模拟研究

本文基于一种并行高精度的静动交接面处理方法,采用了SA模型及基于SA的分离涡模拟DES方法,进行了某压气机静动干涉流动的计算.研究表明对本文算例,在微小分离处,如20%到80%叶高处,DES与SA计算出的流动损失相差很小;而在大分离处,如叶根叶顶处,DES结果与SA差别较大,并且DES可更好地描述涡结构.在叶顶处,DES计算出比SA更强的泄漏流动,导致更大的损失.在叶根处,DES计算出了明显的静叶动态尾迹涡脱落现象,这一现象导致了与SA不一样的损失机理,即脱落涡与动叶头部相撞而产生时序效应,从而使计算损失较小.同时,本文研究结果与之前对孤立静叶的研究是相互验证的.     

N-[(1-芳基-3-苯基-吡唑-4-基)次甲基]-2-羟基苯甲酰肼类衍生物的合成、表征及抑菌活性

依据生物活性叠加原理,以邻羟苯基和苯基吡唑为分子核心,构建了6种未见报道的N-[(1-芳基-3-苯基-吡唑-4-基)次甲基]-2-羟基苯甲酰肼衍生物.以芳胺为原料,经重氮化、还原、与苯乙酮缩合及Vilsmeier-Haack反应制得1-芳基-3-苯基-4-甲酰基吡唑,再与水杨酰肼反应制得目标化合物,其结构经IR,1HNMR和元素分析等验证.探讨了制备中间体(3a～3f)的反应机理,结果表明,1位芳环上取代基对关环反应有显著影响,供电基有利于关环反应的进行,吸电基则恰恰相反.抗菌活性测试表明,质量分数为0.01%的化合物对大肠杆菌和白色念珠菌的抑菌率高达100%,有极强的抑菌活性,对金黄色葡萄球菌的抑菌率达70%以上,有一定的抑菌活性,是一类极具潜力的抗真菌和抗革兰氏阴性菌的化合物.构效分析结果表明,1位芳基中引入Cl和Br等卤原子,能显著增强化合物的抑菌活性,而引入NO2和CH3基团,则会降低其抑菌活性.     

Zirconium complexes containing a diarylamido diphosphine ligand: Structural preferences controlled by ligand electronics and sterics

This work describes the preparation of [PNP]ZrX₃ ([PNP]⁻ = [N(o-C₆H₄PⁱPr₂)₂]⁻; X = Cl, Me, CH₂SiMe₃) whose structural preference is found to be a function of the electronic and steric nature of the monodentate ligand X⁻. The reaction of ZrCl₄(THF)₂ with [PNP]Li in toluene at room temperature generates [PNP]ZrCl₃ as a red solid in 60% yield. Alkylation of [PNP]ZrCl₃ with three equivalents of Grignard reagents in diethyl ether at −35 °C produces cleanly [PNP]ZrR₃ (R = Me, CH₂SiMe₃) as yellow crystalline materials. An X-ray diffraction study of [PNP]ZrCl₃ showed it to be a chloride-bridged binuclear species {[PNP]ZrCl₂(μ−Cl)}₂ in which both zirconium atoms are 7-coordinate whereas that of [PNP]ZrMe₃ revealed a mononuclear, 6-coordinate core structure. Interestingly, with the incorporation of more sterically demanding alkyls, [PNP]Zr(CH₂SiMe₃)₃ is a 5-coordinate compound wherein the amido phosphine ligand is κ²-N,P bound to zirconium. The solution structures of these molecules were also assessed by variable-temperature NMR spectroscopy.     

Mesomorphism and luminescence properties of platinum(II) complexes with tris(alkoxy)phenyl-functionalized pyridyl pyrazolate chelates

A series of new mesomorphic platinum(II) complexes 1 – 4 bearing pyridyl pyrazolate chelates are reported herein. In this approach, pyridyl azolate ligands have been strategically functionalized with tris(alkoxy)phenyl groups with various alkyl chain lengths. As a result, they are ascribed to a class of luminescent metallomesogens that possess distinctive morphological properties, such as their intermolecular packing arrangement and their associated photophysical behavior. In CH₂Cl₂, independent of the applied concentration in the range 10^?6–10^?3 M , all Pt^II complexes exhibit bright phosphorescence centered at around 520 nm, which is characteristic for monomeric Pt^II complexes. In stark contrast, the single‐crystal X‐ray structure determination of [Pt(C4pz)₂] ( 1 ) shows the formation of a dimeric aggregate with a notable Pt???Pt contact of 3.258 Å. Upon heating, all Pt^II complexes 1 – 4 melted to form columnar suprastructures, for which similar intracolumnar Pt???Pt distances of approx. 3.4–3.5 Å are observed within an exceptionally wide temperature range (>250 °C), according to the powder XRD data. Upon casting into a neat thin film at RT, the luminescence of 1 – 4 is dominated by a red emission that spans 630–660 nm, which originates from the one‐dimensional, chainlike structure with Pt–Pt interaction in the ground state. Taking complex 4 as a representative, the emission intensity and wavelength were significantly decreased and blueshifted, respectively, on heating from RT to 250 °C. Further heating to liquefy the sample alters the red emission back to the green phosphorescence of the monomer. The results highlight the pivotal role of tris(alkoxy)phenyl groups in the structural versus luminescence behavior of these Pt^II complexes.